CN1547272A - Method for preparation of lithium manganate having uniform spinel structure - Google Patents

Method for preparation of lithium manganate having uniform spinel structure Download PDF

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Publication number
CN1547272A
CN1547272A CNA2003101106626A CN200310110662A CN1547272A CN 1547272 A CN1547272 A CN 1547272A CN A2003101106626 A CNA2003101106626 A CN A2003101106626A CN 200310110662 A CN200310110662 A CN 200310110662A CN 1547272 A CN1547272 A CN 1547272A
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lithium
spinel structure
lithium manganate
temperature
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CN1286194C (en
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刘务华
阳朝晖
刘怡
徐保伯
胡剑
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HUNAN JINGXIN TECHNOLOGY Co Ltd
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HUNAN JINGXIN TECHNOLOGY Co Ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1391—Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G45/00—Compounds of manganese
    • C01G45/12—Manganates manganites or permanganates
    • C01G45/1221—Manganates or manganites with a manganese oxidation state of Mn(III), Mn(IV) or mixtures thereof
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/30—Three-dimensional structures
    • C01P2002/32—Three-dimensional structures spinel-type (AB2O4)
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/40—Electric properties
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/021—Physical characteristics, e.g. porosity, surface area
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/04—Processes of manufacture in general
    • H01M4/0471—Processes of manufacture in general involving thermal treatment, e.g. firing, sintering, backing particulate active material, thermal decomposition, pyrolysis
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

The invention is a kind of lithium ion cell positive material, which concretely refers to a manufacturing method for a kind of lithium manganic acid material which has an even spinel structure. The invention uses high purity electrolyzation MnO2 or/and chemical MnO2 as materials, the MnO2 with multi-aperture skeleton can be acquired through baking in 500-1000oC, acid processed for 0.5-3 hours in 70-100 oC, the block beforehand mixture; then they are synthesized for 8-30 hours in air under temperature of 700-900 oC, the product can acquired after being cooled and grinded. The material has a large capacity, the electrochemical performance is stable, and the cost is low, especially applicable to the lithium ion cell.

Description

Method for preparing lithium manganate with uniform spinel structure
[ technical field]A method for producing a semiconductor device
The invention belongs to a lithium ion battery anode material, and particularly relates to a method for manufacturing lithium manganate with a uniform spinel structure.
[ background of the invention]
The lithium ion battery is a chemical power supply with excellent performance widely applied in recent years, the anode material of the lithium ion battery is mainly an intercalation compound formed by lithium and transition metal oxide, and lithium manganate (LiMn) with a uniform spinel structure, which has large specific capacity, stable electrochemical performance and low cost2O4) Has the most development potential as the anode material.
The common methods for synthesizing lithium manganate include a solid phase method and a liquid phase method. The solid phase method is a high-temperature synthesis method in which solid manganese compounds and lithium compounds are fully ground, mixed and synthesized for a long time. For example, the preparation method of the anode material of the lithium ion battery with the patent application number of 00117352.9 and the synthesis method of the spinel lithium manganese oxide with stable structure for the lithium ion battery with the patent application number of 01129710.7 have simple process and low cost. However, lithium ions need to diffuse for a long distance and a long time during solid phase synthesis to be inserted into crystal lattices, so that a non-uniform crystallization phenomenon is easily caused, and the uniformity of the product structure is poor.
The liquid phase method, as in the chinese patent application 02100767.5, has the advantages of uniform material mixing, uniform product structure, perfect crystal structure, complex process steps, expensive raw materials and high manufacturing cost.
[ summary of the invention]
The invention aims to overcome the defects of the prior art in cost and performance, solve the problem of uneven structure, and provide a method for manufacturing lithium manganate with an even spinel structure, thereby providing a positive electrode material with even structure, stable electrochemical performance, high specific capacity, low cost and good safety performance for lithium ion batteries, particularly high-capacity lithium ion batteries.
In order to achieve the purpose, the invention provides the following technical scheme:
(1) using high-purity electrolytic manganese dioxide or/and chemical manganese dioxide as raw materials, roasting at the high temperature of 500-1000 ℃ for 0.5-5 hours, adding inorganic acid, stirring at the temperature of 70-100 ℃ for 0.5-3 hours, rinsing precipitates with water, and drying for later use;
(2) adding lithium source substance solution with equal stoichiometric ratio into the pretreated manganese dioxide, fully mixing, aging for several hours, preserving heat under stirring, evaporating and drying to obtain a blocky precursor mixture;
(3) and placing the precursor mixture at a high temperature of 700-900 ℃, carrying out heat preservation and synthesis in an air atmosphere for 8-30 hours, cooling, and carrying out ball milling and crushing to obtain the product.
The invention provides a method for manufacturing lithium manganate with uniform spinel structure, which comprises the following steps: the roasting treatment of the raw materials in the step (1) is to convert the raw materials into Mn partially or completely2O3Acid treatment of Mn2O3Disproportionation, Mn+4In MnO2Form retention, Mn+2Soluble, entering water, thus forming a porous-skeleton type microstructure. The chemical reaction process is as follows:
then, the impurities adsorbed on the surface and in the pores are removed by rinsing, and the pretreated MnO is2The porosity and specific surface area of the porous material are respectively 0.05-0.3ml/g and 15-50m before treatment2The volume per gram is increased to 0.4-1.6ml/g, 80-160m after treatment2The filling space of the lithium source material and the contact area with the lithium source material are greatly increased. In order to facilitate the dissolution of the + 2-valent manganese and the desorption of adsorbed impurities, reduce the residual quantity of impurities in the product as much as possible and consider the treatment cost of materials, the Mn-containing material is treated in the step (1)2O3The acid used for the component oxides of manganese may be H2SO4、HNO3Or H3PO4。
The preparation method provided by the invention comprises the following steps of (2) using soluble lithium salt, adopting a wet mixing method, slowly drying under stirring to remove moisture, and enabling lithium source substances to be in pretreated MnO2The pores and the particle surfaces are crystallized and separated out, and the lithium and the manganese are fully mixed. The lithium source material being LiNO3And LiOH, or a mixture of the LiOH and the LiOH in any proportion.
Since the precursor mixture obtained in step (2) has a lithium compound intercalated into MnO2In the pores, Li generated during high-temperature synthesis in the step (3)+Can quickly enter the pores, effectively shorten the diffusion distance, shorten the synthesis time and improve the uniformity of the lithium manganate material structure.
Compared with the prior art, the invention has the following advantages:
1. the invention converts manganese source substances into MnO with a porous framework structure through pretreatment2Improving the porosity and specific surface area, and adopting a solid-liquid contact wet mixing process to ensure that the lithium source material is MnO of a framework structure2The lithium and the manganese are fully and uniformly mixed, so that the diffusion distance of lithium ions in the synthesis process is shortened, the synthesis rate is accelerated, and the uniformity of the product structure is improved;
2 the lithium manganate material produced by the method is of a uniform spinel structure, has large reversible specific capacity which can exceed 130mAh/g, has stable electrochemical performance, can be charged and discharged with large current, and is suitable for being used as a positive electrode material of a large-capacity lithium ion battery.
3. The manufacturing method provided by the invention has the advantages of simple and easily obtained raw materials, easily controlled process, low production cost, high production efficiency and convenience for realizing large-scale production.
[ description of the drawings]
FIG. 1 is a diagram showing the result of XRD test of lithium manganate synthesized by the method.
FIG. 2 is a graph showing the multiple discharge curves of the lithium manganate material synthesized by the present method.
[ detailed description]embodiments
Example pretreatment MnO2The manufacturing of (1):
weighing 1600g MnO2The percentage content is 92.8, and the bulk density is 2.21g/cm3Particle size ofElectricity of-200 meshesManganese dioxide is decomposed, the manganese dioxide is placed in a muffle furnace, the temperature is raised to 720 ℃, the temperature is kept for 2 hours, the manganese dioxide is taken out and cooled to the room temperature, and brown Mn-containing manganese is obtained2O31376g of the product of (1); then preparing the mixture into slurry according to the solid-liquid ratio of 1: 2, heating the slurry to 85 ℃ under the condition of stirring, and adding 9.5mol of concentrated H2SO4Maintaining at 90-98 deg.C for 2 hr, stopping stirring, naturally cooling and settling, separating, washing with distilled water to pH of 5-6, filtering, and drying at 120 deg.C for 6 hr to obtain pretreated MnO2823g of the product.
For the pretreatment MnO2Powder for testing, MnO thereof291.4 percent, 62.8 percent of Mn and 1.55g/cm of tap density3The specific surface area is 116m measured by the BET method2/g。
Example two a method of manufacturing a lithium manganate material having a uniform spinel structure:
with MnO2The percentage content is 92.5, and the bulk density is 2.27g/cm3Electrolytic manganese dioxide with the particle size of 325 meshes is used as manganese source material, except that the roasting temperature is 800 ℃, the acid is concentrated nitric acid, and the other conditions are the same as the conditions of the pretreatment MnO prepared in the first example2. Tested, its MnO291.2 percent, 62.6 percent of Mn and 1.52g/cm of tap density3. Accurately weighing the pre-treated MnO2100g of analytically pure LiNO, 39.2g of which are added3Adding 80ml of distilled water for gelatinization, aging for 12 hours, and heating and drying while stirring until the material is in a block shape; and then transferring the lithium manganate into a crucible, heating and cooling at the speed of 1 ℃/min, treating at the high temperature of 760 ℃ for 24 hours, cooling, performing ball milling and crushing, and sieving by a 200-mesh sieve to obtain the black lithium manganate serving as the lithium ion battery anode material.
The obtained material is subjected to ICP-AES result analysis, the Li% of the material is 4.1, the Mn% of the material is 61.4, and XRD test shows that the material has a uniform spinel structure and a single chemical composition. The obtained material is used as an anode, a metal lithium sheet is used as a cathode to assemble an experimental battery, charge and discharge tests are carried out in a range of 3.2-4.5V, the first reversible specific capacity is 133mAh/g, and the stable circulating reversible specific capacity is 126 mAh/g.
Example three a method for manufacturing a lithium manganate material having a uniform spinel structure:
accurately weighed 100g of the pretreated MnO prepared as described in example two226.3g of analytically pure LiOH.H are added2Adding 100ml of distilled water for gelatinization, aging for 2 hours, and heating and drying while stirring until the material is in a block shape; and then transferring the lithium manganate into a crucible, heating and cooling at the speed of 1 ℃/min, treating at the high temperature of 760 ℃ for 10 hours, cooling, performing ball milling and crushing, and sieving by a 200-mesh sieve to obtain the black lithium manganate serving as the lithium ion battery anode material.
XRD test shows that the obtained material has single chemical composition and homogeneous spinel structure. The obtained material is used as the anode, the metal lithium sheet is used as the cathode to assemble an experimental battery, and the charging and discharging test is carried out in the range of 3.0-4.5V, so that the first inverse specific capacity of the material is 99mAh/g, and the cycle capacity reduction rate of the previous 10 cycles is 0.3%.
Example four a method of manufacturing a lithium manganate material having a uniform spinel structure:
pure LiNO for analysis of lithium source removing substance3Except that the mass was 37.5g, lithium was obtained under the same conditions as in example IIThe lithium manganate is used as the anode material of the ion battery.
The obtained material was subjected to ICP-AES results analysis, whereby it was found that the material had Li% of 3.9 and Mn% of 61.4. The obtained material is used as an anode, a metal lithium sheet is used as a cathode to assemble an experimental battery, a charge-discharge test is carried out in a range of 3.2-4.5v, the first reversible specific capacity is 128mAh/g, and the average reversible specific capacity of the previous 3 cycles is 126 mAh/g.

Claims (3)

1. A method for producing lithium manganate having a uniform spinel structure, characterized by comprising the steps of:
(1) high-purity electrolytic manganese dioxide or/and chemical manganese dioxide are/is used as manganese source materials, the high-temperature roasting is carried out for 0.5 to 5 hours at the temperature of 500 to 1000 ℃, then inorganic acid is added, the stirring treatment is carried out for 0.5 to 3 hours at the temperature of 70 to 100 ℃, precipitates are rinsed by water, and the precipitates are dried for later use;
(2) adding lithium source substance solution with equal stoichiometric ratio into the pretreated manganese dioxide, fully mixing, aging for several hours, slowly evaporating and drying under the stirring condition to obtain a blocky precursor mixture;
(3) and placing the precursor mixture at a high temperature of 700-900 ℃, carrying out heat preservation and synthesis in an air atmosphere for 8-30 hours, cooling, and carrying out ball milling and crushing to obtain the product.
2. The method of producing lithium manganate having uniform spinel structure as set forth in claim 1, wherein said inorganic acid in the step (1) of the production method is H2SO4Or HNO3Or H3PO4。
3. The method of claim 1, wherein the lithium source material in the step (2) is LiNO3Or LiOH or a mixture thereof in any proportion.
CNB2003101106626A 2003-12-16 2003-12-16 Method for preparation of lithium manganate having uniform spinel structure Expired - Fee Related CN1286194C (en)

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102050494A (en) * 2010-11-04 2011-05-11 中信大锰矿业有限责任公司 Preparation method of lithium manganate precursor of Li-ion power battery
CN101248010B (en) * 2005-03-30 2011-06-01 Sk能源株式会社 Process of precipitation for spheric manganese carbonate and the products produced thereby
CN102738460A (en) * 2012-07-17 2012-10-17 中国电子科技集团公司第十八研究所 Surface passivating treatment method of spinel type manganese-based positive pole material
CN102903903A (en) * 2012-09-27 2013-01-30 中国海洋石油总公司 Preparation method of lithium battery cathode material high-purity lithium manganese oxide
CN103268937A (en) * 2013-05-15 2013-08-28 陕西科技大学 Preparation method of framework lithium manganate battery cathode material
CN103560242A (en) * 2013-11-07 2014-02-05 广西桂柳化工有限责任公司 Device for processing electrolytic manganese dioxide of lithium ion battery

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101248010B (en) * 2005-03-30 2011-06-01 Sk能源株式会社 Process of precipitation for spheric manganese carbonate and the products produced thereby
CN102050494A (en) * 2010-11-04 2011-05-11 中信大锰矿业有限责任公司 Preparation method of lithium manganate precursor of Li-ion power battery
CN102738460A (en) * 2012-07-17 2012-10-17 中国电子科技集团公司第十八研究所 Surface passivating treatment method of spinel type manganese-based positive pole material
CN102903903A (en) * 2012-09-27 2013-01-30 中国海洋石油总公司 Preparation method of lithium battery cathode material high-purity lithium manganese oxide
CN103268937A (en) * 2013-05-15 2013-08-28 陕西科技大学 Preparation method of framework lithium manganate battery cathode material
CN103560242A (en) * 2013-11-07 2014-02-05 广西桂柳化工有限责任公司 Device for processing electrolytic manganese dioxide of lithium ion battery

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